Shaped structures of acrylonitrile polymers with permanent antistatic properties

ABSTRACT

The invention relates to acrylonitrile polymers which contain as an antistatic additive at least one compound of the general formula   D R A W I N G

United States Patent 1 Bentz et a1.

[ 1 Oct. 7.1975

[ 1 SHAPED STRUCTURES OF ACRYLONITRILE POLYMERS WITH PERMANENT ANTISTATIC PROPERTIES [75] lnvenmrs: Francis Bentz, Cologne; Giinther Nischk. Dormagen both of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen-Bayerwerk, Germany 221 Filed: Sept. 6. I974 [21] App1,N0.:S03,768

[30] Foreign Application Priority Data Sept. 15, 1973 Germany 1. 2346566 [56] References Cited UNITED STATES PATENTS 3,852255 12/1974 Bentz 260/326 N 3,856.738 12/1974 Bodcshcim .v 260/316 N Primary ExaminerPau| R. Mich] Attorney, Agent, or FirmPlum1ey & Tyner [57] ABSTRACT The invention relates to acrylunitrile polymers which c0ntain as an antistatic additive at least one compound of the general formula 4 Claims, N0 Drawings SHAPED STRLCTL'RES OF ACRYLONITRILE POLYMERS WITH PERMANENT ANTISTATIC PROPERTIES This imention relates to shaped structures. in particular filaments. fibres and sheets of acrylonitrile polymers which have permanent antistatic properties. and a process for producing them.

Shaped structures of synthetic polymers. e.g. fibres of polyacrylonitrile. generally suffer from disadvantage of to general formula I t) R" H becoming electrostatically charged. This charging C- wherein curs when the surface resistance of the fibre is more than it) Ohm.

Numerous processes for reducing the electrostatic charge on shaped structures of this type have already been described in the literature, for example the electrical conductivity may be increased by treating the surface of the fibres or of the textile produced there from with antistatic dressings. The antistatic effect obtained in this way. however, is often not resistant to washing.

As described. for example, in German Offenlegungsschriften Nos. l,469.9l3 and 1,965.63], an antistatic finish may be obtained by applying aqueous solutions of suitable substances to fibres which are in the aquagel state. Another method frequently employed for reducing the electrostatic charges on shaped structures of synthetic polymers involves the addition of polyethers or other suitable compounds to the solution or melt of these polymers before they are shaped. Most of the ad ditives. however, have the disadvantage of not being wash-resistant.

It has already been proposed to render polyacrylonitrile fibres permanently antistatic without reducing their light fastness by adding thereto compounds ob tained by reacting ethoxylated alcohols with diisocyahates.

it has now been found that compounds which contain a urea group in addition to a polyether group and two urethane groups impart an even better antistatic finish to polyacrylonitrilc fibres.

It is, therefore. an object of this invention to provide shaped articles of acrylonitrile polymers which exhibit an improved antistatic behaviour.

Other objects will be evident from the description and the Examples.

These objects are accomplished by a Shaped structure of an acrylonitrile polymer consisting of from 85 to 99.5%. by weight. of polyacrylonitrile or an acrylonitrilc copolymer containing at least 60% of copolymerised acrylonitrile comprising as an antistatic additive from 0.5 to I59 by weight. of a polyether diurethane urea compound of the following general formula l (1 J ll R Ot wherein R denotes a (I. alk-y]. cycloalkyl. acryl. aralkyl or alkaryl group. any of which may be substituted by halogen or alkyl; denotes an integer of from 5 to 50; R denotes an alkylcne. arylene. aralkylene. alkarylenc or cycloalkylene group; and

R denotes a C C alkyl. cycloalkyl. aryl, aralkyl or alkaryl group. any of which groups may be substituted by halogen or alkyl;

.\ denotes an integer of from S to R denotes an alkylene, arylene, aralkylene. alkarylene or cycloalkylene group; and

R" denotes hydrogen or a methyl group. to the solution of said acrylontrile polymer in an organic solvent and removal of said solvent in a shaping operation.

The polyethers used according to the invention which contain two urethane groups and one urea group have excellent compatibility with the polymers. They have very high wash resistance due to the presence of the urea group and impart excellent antistatic characteristics to the acrylonitrile polymer fibres to which they have been added.

By the term "shaped structures" is meant primarily filaments, fibres and sheets. The polyether diurethane urea compounds are preferably added in a quantity of from 2 to l()/(. by weight. based on the polymer mixture. The term acrylonitirle polymers inlcudes. in particular, polyacrylonitrile or copolymers of acrylonitrile with (meth )acrylic acid esters, such as methyl and ethyl acrylate and methacrylate; (meth)acrylamides. e.g. (meth)acrylamide and N,N-dimethyl- (meth )acrylamide; N vinyl lactams. e.g. N vinylpyrrolidones; vinyl esters or ethers; (methlallyl esters; or ethers; vinyl or vinylidene halides. eg. vinyl or vinylidene chloride and vinyl or vinylidene bromide; alkylvinyl pyridine. eg. N-vinyl-4methylpyridine; vinyl imidazoles; mono or di-alkylamino alkylacrylates or methacrylates. e.g. dimethylaminoethyl (meth )acrylate or quaternized derivatives thereof; vinyl or allyl or methallylsulphonic acids; and vinyl. allyl or methallylphosphonic acids or their esters. which contain at least by weight. acrylonitrile in a copolymerised form.

To prepare the above additives. polyether monourethanes with a free isocyanate group are prepared in known manner by reacting aliphatic alcohols or phenols. such as nonan-l-ol, dodecan-l-ol. myristyl alcohol, cetyl alcohol. stearyl alcohol or i-nonyl phenol, in

the melt with alkylenc oxides, preferably ethylene oxide. in the presence of a basic catalyst. eg. an alkali metal hydroxide. The reaction is preferably carried out using I mol of the alcohol or phenol and from 5 to 50. preferably from it) to 35. mol of the alkylene oxide. The polyalkoxylated alcohols obtained in this way may easily be reacted with diisocyanates in a one pot process, preferably after determining the OH number. The reaction is either carried out in the absence of a solvent a lempemturc of from 70am l5OQC- p flask equipped with stirrer and reflux condenser. After 90to l30C, or in an inert solvent. suc 115 dimethyl displacement of air in the flask with nitrogen, ethylene folnldmillleat similar tempemtme- The molar ratio of 5 oxide is introduced at l00C until a weight increase of alkoxylaled alcohol to dlisocyanme p y is P 1320 parts, by weight is obtained. The molecular ably from 1:1 to l:l.2. The reaction time is from /2 to weight is f d by determining the OH number. 0H9 l2 hours, preferably from to 7 hours. A compound 0 molecular weight having free lsocyimale P- Corresponding m the This polyether is neutralised by adding 60 parts, by following general formula ll is obtained initially, to i h f pure acetic id to 1592 parts, by weight, f O polyether and heating to l00C for l hour. Excess acetic acid is then evaporated ofi under the vacuum obtainable using a water-jet at an oil bath temperature of wherein 100C. 250 parts, by weight, 4,4-diphenylmethane- R, R R and x are as defined above. diisocyanate are introduced gradually at this tempera- The diisocyanates used are prefera ly hexamethylture, with a small nitrogen flush. Stirring is then continene diisocyanate. cyclohexzme-l.4- i 0 y n 3- ued for l0 hours at from I to lC. l300 parts, by isocyanato-methyl-3,5.S-trimethyl-cyclohexane isocyavolume, DMF are then added. 25 parts, by volume, of nate, phenylene-l ,3 -diisocyanate, phenylene-l,4- water are added dropwise to the resulting solution diisocyanate, diphenylmethane-4,4'-diisocyanate and 20 which is then stirred for 5 hours at lC. 2,2-bis-(4-isocyanatophenyl)-propane. b. Production and examination of polyacrylonitrile The urea derivative is obtained from the compounds fibre. The solution from Example la is used to prepare with free isocyanate group in a one pot process by the a 29% dimethyl formamide solution consisting of a mixaddition of the stoichiometric quantity of water. After ture of 90%, by weight, of an acrylonitrile copolymer the addition ofwater, the reaction mixture is stirred for 25 (93.5% acrylonitrile, 5.5% by weight, methyl methacseveral hours at elevated temperature to complete the rylate and 171, by weight, methacryloylaminobenzenereaction. disulphimidebenzene) with K-value of 80 and I070, by The polyether diurethane ureas are added either in weight, of the polyethylene oxide diurethane urea. This solid form or, preferably, in a solution of the spinning solution was dry-spun at a viscosity of from to solution of the acrylonitrile polymer. It is particularly 3U ball-falling-seconds at 80C, (determined by the falling preferred to prepare the additives in dimethylformball method by which the falling-time of a ball of V2- amide so that the solution of the required quantity of steel according to DIN 540! between two markings the resulting compounds may be added directly to the which have a distance of 7 cm from each other is measpinning solution of polyacrylonitrile. sured in a tube having an internal diameter of 3 cm and The surface resistance of the shaped product, in par- 35 being filled with the solution to be determined). Thickticular fibres, was determined as indicated in the Examness of fibre: 3.3 dtex. ples. using a commercial high resistance Ohmmeter be- The antielectrostatic effect of the additive was detertween the plates of two electrodes l cm apart at a meamined by measuring the surface resistance of the fibre suring voltage of l()() V in accordance with proposed at 3C and 50% relativ humidity. Sample after l0 standard DlN 54 345. Before each determination, the washings; l 3 0!)- Sample after dyeing and three fibres were conditioned in a standard atmosphere of ng I 6 X l0 0. 50% relative humidity at 23C for 72 hours.

Fibres produced according to the invention have an electrical surface resistance of from 10" to l0 Ohm at 50% relaive humidity and 23C. 45

370 parts. by weight, of stearyl alcohol and 4 parts, by weight, NaOH are introduced into a three-necked EXAMPLE 2 a. Preparation of Using the method indicated in Example la, 270 parts, by weight, stearyl alcohol are reacted with ethylene tielectrostatic character being thereby diminished. oxide at I00C in the presence of 4 parts, by weight, [n the following Examples which are to further illus- NaOH until a weight increase of 924 parts, by weight, trate the invention without limiting it, parts by weight 60 i obt i d (011% 1,42), After treatment with 60 are related to parts by volume as kilogram to litre. parts, b i ht, f pure ti id and re oval of the EXAMPLE 1 excess acetic acid in a vacuum, parts, by weight,

a. Preparation of 4.4'-diisocyanatodiphenyl methane are added gradu- The fibres according to the invention may be dyed with the conventional dyes without their excellent anally to 601 parts. by weight. of the polyether at 100C. The reaction mixture is then stirred for 10 hours at 130C. 1000 parts, by volume, dimethyl formamide are then added. A mixture of 50 parts, by volume, DMF and 12.5 parts, by volume, water are added dropwise to the resulting solution. The reaction mixture is then stirred for 3 hours at 140C to complete the reaction.

b. Production and examination of polyacrylic fibre.

This solution is used to prepare a 29% dimethylformamide solution which consists 95%, by weight, of an acrylonitirle copolymer which has the composition indicated in Example 1b and a K-value of 81 and 5%, by weight. of the polyethylene oxide diurethaneurea from Example 221. The solution (viscosity from 75 to 80 ballfalling-seconds at 80C) was dry-spun. Thickness of tibre: 3.3 dtex.

Electrical surface resistance after washings: 1 X111 Q. After dyeing and 3 washings: 6 X10 (1.

EXAMPLE 3 a. Preparation of 704 parts. by weight, ethylene oxide are added to 170 parts, by weight, stearyl alcohol in the presence of 4 parts, by weight, NaOH at 100C as indicated under 1a. OH7( 1.74.

After treatment with 60 parts, by weight, acetic acid and removal of excess acetic acid under vacuum, 250 parts. by weight, 4,4-diphenylmethane-diisocyanate are added to the melt at 100C. The temperature is maintained at 130C for 10 hours. A mixture of 50 parts, by volume, DMF and 30 parts, by volume, water is added dropwise to the solution after the addition of 2000 parts, by volume, DMF. The mixture is then stirred for 7 hours at 150C.

b. Production and examination of polyacrylic fibre.

The solution from Example 321 is used to prepare a 29V: dimethylformamide solution consisting of a mixture of 925 parts, by weight, of an acrylonitrile copolymer which has the composition indicated in Example lb and a K-value of 82, and 7.5 parts, by weight, of the polyethylene oxide diurethane urea. The viscosity is approximately 80 ball-falling-seconds at 80C. Thickness of the fibre; 3.3 dtex.

The electrical surface resistance of the fibre was determined at 23C and 509? relative humidity. Sample after 10 washings: 6 X 10"!) After dyeing and 3 washings: Z X 10 {1.

(H lCH ),,O(CH CH,O);, C--NH R wherein R CH. 21.-

2O CH:i H

In a similar way to that indicated in Example la 270 25 parts. by weight, stearyl alcohol and 4 parts, by weight,

EXAMPLE 4 a. Preparation of NaOH solid are introduced into a reaction vessel and 1400 parts, by weight, ethylene oxide are introduced into the melt at about C and absorbed (OH 1.01 After treatment with acetic acid and concentration by evaporation under vacuum, 841 parts, by weight, of this product are mixed with 111 parts, by weight, 3-isocyanatomethyl-3,-5,5trimethylcyclohexane isocyanate at 100C. The mixture is then stirred for 8 hours at from l20to C. 1000 parts, by volume, DMF are then added. 50 parts, by volume, DMF and 14 parts, by volume, water are then introduced dropwise. The reaction mixture is then stirred for 7 hours at from l40to C to form the corresponding urea.

b. Production and examination of the polyacrylic fibre.

The solution from Example 4a is used to prepare a 29% dimethylformamide solution which ccnsists of a mixture of 92.5%, by weight, of an acrylonitrile copolymer which has the composition indicated in Example lb and a K-value of 81, and 7.5%, by weight, of the polyethylene oxide diurethane urea. The viscosity determined by the falling ball method: from 75 to 80 ballfalling-seconds at 80C. The solution is dry-spun.

Thickness of the fibre: 3.3 dtex.

The antielectrostatic effect of the additive is determined by measuring the electrical surface resistance of the fibre at 23C and 50% relative humidity. Sample after 10 washings: 5 10*(1 After dyeing and 3 washings: l X 1() (1 EXAMPLE 5 a. Preparation of CH. CH=- The ethoxylation of stearyl alcohol is carried out described in Example 2a. 111 parts, by weight, 3- isocyanatomethyl-3,5.S-trimethyl-cyclohexane isocyanate are added dropwise to 60l parts, by weight, of the ethoxylated stearyl alcohol at lC. The reaction mixture is then stirred for 10 hours at about l30C. The melt is then taken up in l000 parts, by volume, DMF and a mixture of 50 parts, by volume, DMF and l2.5 parts, by volume, water is introduced dropwise. The reaction mixture is then stirred for a further 7 hours at from [40 to I50C.

b. Production and examination of polyacrylic fibres. The solution from Example 5a is used to prepare a 29% dimethylformamide solution which consists of a mixture of 90 parts, by weight, of an acrylonitrile copolymer which has the composition indicated in Example lb and a K-value of 85, and i0 parts, by weight of the additive. The viscosity of the spinning solution is determined as being from 75 to 80 ball-falling-seconds at 80C, using the falling ball method. The fibre is spun dry.

Thickness of fibre: 3.3 dtex.

The electrical surface resistance of the fibre is determined at 23C and 50% relative humidity. After washings: 7 X 10 (1.

After dyeing and 3 washings: 3 X I0 Q.

EXAMPLE 6 a. Preparation of l' CO NH ucH. 1.701 cH cH o ),.,CNH R/ wherein R Stearyl alcohol is reacted with ethylene oxide as indicated in Example 3a. 56 parts, by weight, 3-

isocyanatomethyl-3,5.S-trimethylcyclohexane is isocyanate are added to 245 parts, by weight, of the ethoxylated product at about 100C and the mixture is heated to 130C for 8 hours. After the addition of 500 parts, by volume, DMF a mixture of 50 parts, by volume. DMF and 7 parts, by volume, water is introduced dropwise and the reaction mixture is then stirred for 7 hours at 150C.

b. Production and exanination of the polyacrylonitrile fibres.

The solution from Example 6a is used to prepare a 2971 dimethylformamide solution which is composed of a mixture of 90% by weight, of acrylonitrile copolymer having the composition indicated in Example lb and a K-value of 80, and 10% by weight, of the additive pre pared under 6a. The solution, which has a viscosity of from to ball-falling-seconds at 80C. (determined by the falling ball method), is spun dry.

Thickness of fibre: 3.3 dtex The electrical surface resistance of the fibre is determined at 23C and 50% relative humidity.

Sample after l0 washings: l X l0 0.

After dyeing and 3 washings: 7 X l0 (2.

I claim:

1. A shaped structure of an acrylonitrile polymer consisting of from to 99.5% by weight, of polyacrylonitrile or an acrylonitrile copolymer containing at least 60% of copolymerised acrylonitrile comprising as an antistatic additive from 0.5 to 15%, by weight, of a polyether diurethane urea compound of the following general formula I RO(CH*CH. ,O],i -NHR'NH -NHRNH O R C iOCHAH OR (I) wherein R denotes a C C -alkyl. cycloalkyl, aryl, aralkyl or alkaryl group, any of which may be substituted by halogen or alkyl; .t denotes an integer of from 5 to 50;

R denotes an alkylene, arylcne, aralkylene, alkarylene or cycloalkylene group; and R" denotes hydrogen or a methyl group.

2. lhe shaped structure of claim I, wherein in the weight, (based on the polymer mixture), of a polyether general formula (I) the group R represents diurethane urea compound corresponding to general formula l i R" O R-()(H-CH- ),,l -NHR'NH-C-NH-RNH- ('H H 0 1* v r i locn H OR (I;

wherein 3. The shaped structure of claim I, wherein in the R denotes a C C -alkyl, cycloalkyl, aryl, aralkyl or general formula (I) the group R represents alkaryl group. any of which groups may be substituted by halogen or alkyl; x denotes an integer of from 5 to 50;

R denotes an alkylene, arylene aralkylene a]kary lene or cycloalkylene group; and

R" denotes hydrogen or a methyl group; 4. A process for the production ofa shaped structure to the solution of said acrylonitrile polymer in an orof an acrylonitrile polymer with antistatic additives ganic solvent and removal of said solvent in a shaping which comprises addition of from 0.5 to l57r, by operation, 

1. A SHAPED STRUCTURE OF AN ACRYLONITRILE POLYMER CONSISTING OF FROM 85 TO 99.5%, BY WEIGHT, OF POLYACRYLONITRILE OR AN ACRYLONITRILE COPOLYMER CONTAINING AT LEAST 60% OF COPOLYMERISED ACRYLONITRILE COMPRISING AS AN ANTISTATIC ADDITIVE FROM 0.5 TO 15%, BY WEIGHT OF A POLYETHER DIURETHANE UREA COMPOUND OF THE FOLLOWING GENERAL FORMULA I
 2. The shaped structure of claim 1, wherein in the general formula (I) the group R'' represents
 3. The shaped structure of claim 1, wherein in the general formula (I) the group R'' represents
 4. A process for the production of a shaped structure of an acrylonitrile polymer with antistatic additives which comprises addition of from 0.5 to 15%, by weight, (based on the polymer mixture), of a polyether diurethane urea compound corresponding to general formula I 